US5500332A - Benzotriazole based UV absorbers and photographic elements containing them - Google Patents

Benzotriazole based UV absorbers and photographic elements containing them Download PDF

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US5500332A
US5500332A US08/430,939 US43093995A US5500332A US 5500332 A US5500332 A US 5500332A US 43093995 A US43093995 A US 43093995A US 5500332 A US5500332 A US 5500332A
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photographic element
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absorbing compound
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Lal C. Vishwakarma
Glenn Brown
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Eastman Kodak Co
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Priority to EP96420123A priority patent/EP0740198B1/en
Priority to JP8105832A priority patent/JPH08304957A/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/134—Brightener containing

Definitions

  • This invention relates to particular benzotriazole based UV absorbing compounds, and to photographic elements containing such compounds.
  • UV radiation as used in this application means light having a wavelength of 300-400 nm.
  • UV sensitivity is usually undesirable in that it produces an image on the photographic element which is not visible to the human eye.
  • the image dyes in the color photographs are known to fade due to action of UV light.
  • other organic molecules such as unused color forming couplers in the emulsion layers and optical brighteners in the paper support degrade due to action of UV light and generate undesirable color stains on the finished photographs. Therefore, photographic elements typically contain a UV absorbing compound (sometimes referred to simply as a "UV absorber").
  • UV absorbers Another function of UV absorbers is to prevent the formation of undesirable patterns caused by electrostatic discharge in silver halide photographic materials. In general, UV absorbers impart light stability to organic molecules in various products which are susceptible to degrade as a result of the action of UV.
  • an effective UV absorber should have its peak absorption above a wavelength of 320 nm.
  • the absorption peak may be at a longer wavelength, as long as absorption drops off sufficiently as it approaches the visual range (approximately 400 to 700 nm) so that no visible color is shown by the compound.
  • a UV absorber should have a high extinction coefficient in the desired wavelength range. However, for the most desirable UV protection, the high extinction coefficient should be at those wavelengths sufficiently below the visual range so that the compound should not be visually yellow.
  • UV absorbers of the benzotriazole class for photographic and other applications are well known. They include hydroxyphenyl benzotriazoles with various substituents on the hydroxyphenyl ring, including alkoxy. Compounds of the foregoing type are disclosed, for example, in Japanese published patent application JP 3139589.
  • U.S. Pat. No. 5,112,728 discloses photographic elements with liquid hydroxyphenyl benzotriazole UV absorbers, including one example which incidentally has a racemic carbon center.
  • U.S. Pat. Nos. 4,975,360; 4,973,701 and 4,996,326 all disclose photographic elements which contain liquid hydroxyphenyl benzotriazoles as UV absorbers.
  • U.S. Pat. Nos. 4,973,701 and 4,992,358 discuss various advantages of the absorbers being liquid. Some of the compounds in those patents include substituents on the hydroxyphenyl ring which incidentally have a racemic carbon center.
  • 2-Hydroxyphenyl benzotriazole UV absorbers with a large class of acylamino groups including carbamates, sulfonamides, and many others, are described in FR 1,330,378, FR 1,324,898, FR 1,324,897, GB 991 204, GB 991 320, GB 991 142, GB 991 630, and GB 991 204.
  • FR 1,330,378, FR 1,324,898, FR 1,324,897 GB 991 204, GB 991 320, GB 991 142, GB 991 630, and GB 991 204.
  • none of the compounds disclosed in those references provide a carbamate with an asymmetric carbon.
  • UV absorbers which are currently used in photographic products include those of formula (II-A) and (II-B) below: ##STR2## However, compounds (II-A) and (II-B) have a propensity to crystallize out during cold storage of a dispersion of them.
  • UV absorbing compounds suitable for photographic uses which are relatively stable in a photographic environment, and in particular have a low tendency to crystallize out at ordinary temperatures at which photographic elements are used and/or stored, which have a high extinction coefficient so that less of it needs to be used to obtain the same UV absorption, and which have a good UV absorption spectrum for photographic uses.
  • the present invention provides ultraviolet absorbing compounds of formula (I) below, and photographic elements containing them: ##STR3## wherein: R 4 is H or an alkyl group, and the benzo or phenyl ring shown may be further substituted or unsubstituted;
  • X is --C(O)O-- wherein the carbonyl carbon is bonded to the N of NR 4 , or X is --SO 2 --;
  • L is a bivalent linking group
  • p is 0 or 1;
  • A* is an alkyl group having an asymmetric carbon or silicon atom, and
  • ultraviolet absorbing compound of formula (I) is a mixture of two enantiomers about the asymmetric carbon or silicon of A*.
  • UV absorbing compounds of formula (I) have a wavelength of maximum absorption (" ⁇ max") which is desirable in the longer UV region (336-380 nm), have a sharp dropping absorption profile at wavelengths slightly shorter than 400 nm making them useful with known fluorescent brighteners, are relatively stable in the environment of a photographic element, do not readily crystallize in photographic elements, and have high extinction coefficients.
  • ⁇ max wavelength of maximum absorption
  • FIG. 1 shows the normalized absorption spectra in methanolic solution for a mixture of comparative control compounds II-A and II-B (solid line), as well as for the inventive compound V (dotted line);
  • FIG. 2 shows the absorption spectra of coatings in a photographic element of inventive compound V and the comparative compounds II-A and II-B, in total transmission mode, as described below.
  • reference to ultraviolet or UV in relation to the present invention refers to the wavelength range of 300 to 400 nm unless the contrary is indicated.
  • reference to "under”, “above”, “below”, “upper”, “lower” or the like terms in relation to layer structure of a photographic element is meant the relative position in relation to light when the element is exposed in a normal manner. "Above” or “upper” would mean closer to the light source when the element is exposed normally, while “below” or “lower” would mean further from the light source. Since a typical photographic element has the various layers coated on a support, “above” or “upper” would mean further from the support, while “below” or “under” would mean closer to the support.
  • any chemical "group” (such as alkyl group, aryl group, heteroaryl group, and the like) includes the possibility of it being both substituted or unsubstituted (for example, alkyl group and aryl group include substituted and unsubstituted alkyl and substituted and unsubstituted aryl, respectively).
  • substituent groups usable on molecules herein include any groups, whether substituted or unsubstituted, which do not destroy properties necessary for the photographic utility. It will also be understood throughout this application that reference to a compound of a particular general formula includes those compounds of other more specific formula which specific formula falls within the general formula definition.
  • enantiomers have identical structural formulas except they are non-superimposable mirror images of one another. Further, in reference to enantiomeric mixtures, proportions are in mole ratios.
  • the ultraviolet absorbing compound of formula (I) being a mixture of two enantiomers about the asymmetric carbon or silicon of A*, this refers to a mixture of the two optical isomers about the racemic carbon or silicon of A* with R and S stereochemical configurations.
  • the bivalent linking group L may, for example, be an alkylene group having a chain of 2 to 20 atoms in length, with or without intervening oxygen, sulfur or nitrogen atoms.
  • the carbon atoms of L are all saturated. This means that none of the carbon atoms of L would have any type of carbon-carbon double or triple bonds. Thus, in this situation L would not have groups such as --C ⁇ C-- or --C.tbd.C--.
  • L would not have groups such as --C ⁇ C-- or --C.tbd.C--.
  • L could be a group such as (A) below: ##STR4##
  • L may have from 1 to 20 carbon atoms (or 1 to 10, 1 to 6, or 1 to 3 carbon atoms).
  • L may particularly be an alkylene group.
  • L may be unsubstituted or substituted with, for example, a 1 to 10 carbon alkoxy (or 1 to 6, or 1 to 2 carbon alkoxy), a 1 to 10 carbon atom alkyl sulfide (or 1 to 6, or 1 to 2 carbon alkyl sulfide), 0 to 10 carbon amino (or 0 to 6, or 0 to 2 carbon amino), or halogen.
  • L may contain intervening oxygen, sulfur or nitrogen atoms, such as 1 to 5 atoms of any of the foregoing type (or 1 or 2 intervening atoms selected from oxygen, sulfur or nitrogen atoms).
  • L being substituted includes the possibility of the substituents forming a ring.
  • L could then include an alicyclic or heterocylic ring (such as a 3 to 10 or 4, 5, or 6, membered ring).
  • the ring is heterocyclic it may contain, for example, have 1, 2, or 3 heteroatoms (which may be the same or different) selected from 0, S or N.
  • rings as part of L include cyclohexyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl or piperidinyl, although less preferably such rings could also include benzo, pyrrolo, furyl, thienyl, pyridyl or spiro-ether containing rings.
  • L may include as a substituent, particularly when L is an alkylene group as described (that is with or without the intervening heteroatoms described), an ether or ester containing group.
  • the ether or ester containing substituent in L may be of the formula R 8 --O--(R 9 ) n -- or R 8 C(O)--(R 9 ) n - , where R 8 and R 9 are, independently, an alkyl group and n is 0 or 1.
  • R 9 may have, for example, 1 to 6 carbon atoms, while R 8 may have, for example, 1 to 20 carbon atoms (for example, 1 to 10, or 6 to 10).
  • the benzo ring and the hydroxy substituted phenyl ring may each be further substituted. For example, either may have 1 to 4 further substituents.
  • Substituents may, for example, independently be, 1 to 18 carbon alkyl (or 1 to 6, or 1 to 2 carbon alkyl), aryl (such as 6 to 20 carbon atoms), heteroaryl (such as pyrrolo, furyl or thienyl), aryloxy (such as 6 to 20 carbon atoms) alkoxy (such as 1 to 6 or 1 to 2 carbon alkoxy), cyano, or halogen (for example F or Cl, particularly having Cl on the benzo ring at the 5 and/or 6 position, and/or on the hydroxy substituted phenyl at the 5' positon).
  • Substituents for the benzo ring can also include ring fused thereto, such as a benzo, pyrrolo, furyl or thienyl ring. Any of the alkyl and alkoxy substituents may have from 1 to 5 (or 1 to 2) intervening oxygen, sulfur or nitrogen atoms, including or not including asymmetric centers.
  • R 4 is preferably H.
  • R 4 when R 4 is an alkyl group, it may have, for example, from 1 to 20 C atoms (or 1 to 10 or 1 to 6 carbon atoms, such as methyl, ethyl, primary or secondary propyl, or butyl or pentyl either of which may be normal, secondary or tertiary).
  • Substituents include alkoxy (particularly 1 to 6 carbon atoms), halogen (particularly Cl and F), and cyano.
  • R 4 is an alkyl group though, it is preferably an electron withdrawing alkyl group.
  • R 4 When R 4 is not an electron withdrawing alkyl group, there may be a hypsochromic shift (shift to a shorter wavelength) in the wavelenght of maximum UV absorption of a formula (I) compound, as well as a lower molar extinction coefficient (versus the case when R 4 is H). If desired, in such case the wavelength of maximum UV absorption may be again shifted longer by providing a substituent for R 1 or R 2 on the benzo ring of the benzotriazole, which has an unshared electron pair.
  • substituents include Cl, F, dialkylamino, or an alkoxy.
  • Electron withdrawing substituents in general these are discussed in March, Advanced Organic Chemistry, 3rd Ed., J. March, (John Wiley Sons, NY; 1985) at pages 20-21, 228-229, 386-387, 494-497.
  • preferred electron withdrawing substituents in each case described herein, or an electron withdrawing alkyl group for R 4 would have a Hammett ⁇ p constant of greater than 0 (or greater than 0.1 or even 0.3) and preferably between 0.1 to 1.0 (for example, between any of 0.3, 0.4, 0.5 or 0.6 to 1.0).
  • Hammett ⁇ p values are discussed in the foregoing Advanced Organic Chemistry.
  • any alkyl group with an asymmetric carbon atom could be used. With the appropriate substituents on the asymmetric carbon, A* may have as little as only 1 carbon atom. Examples of A* could include However, the asymmetric carbon atom will preferably have at least three different alkyl groups, which means that A* will therefore preferably have at least 4 carbon atoms. A* may have 1 to 20 C atoms (or preferably 4 to 20 C atoms, 4 to 10 or 4 to 6 carbon atoms). A* is preferably of the structure --CR 5 R 6 R 7 as shown below in structure (Ia).
  • the compounds of formula (I) may particularly be of formula (Ia) below (some of carbon atoms on the rings being numbered in formula (Ia) to illustrate how the positions on the rings of benzotriazoles are identified in this application): ##STR5## or more particularly of formula (Ib): ##STR6##
  • R 1 , R 2 and R 3 may be, independently, 1 to 18 (or 1 to 10, 1 to 6, or 1 to 2) carbon alkyl or alkoxy either of which may have 1-5 (or 1 or 2) intervening oxygen, sulfur or nitrogen atoms, or are aryl, heteroaryl, or aryloxy.
  • R 3 may also be a 6'-hydroxy substituent.
  • R 1 , R 2 and R 3 may also be, independently any of the foregoing substituted with 1 to 17 (or 1 to 10, 1 to 6, or 1 or 2) carbon alkoxy, 1 to 17 (or 1 to 10, 1 to 6, or 1 or 2) carbon alkyl sulfide, 0 to 17 carbon amino (or 0 to 10, 0 to 6, or 0 to 2), or a halogen, or any of R 1 , R 2 or R 3 may be H or a halogen (particularly chloro or fluoro) or both R 1 and R 2 together form a 5 to 18 carbon atom aryl group (such as a benzo ring) or heteroaryl ring group (for example, pyrrolo, furyl, thienyl, pyridyl).
  • Substituents on the foregoing rings formed by R 1 and R 2 may include a 1 to 17 (or 1 to 10, 1 to 6, or 1 or 2) carbon atom alkyl or alkoxy, or a halogen.
  • R 1 , R 2 and R 3 may also be, independently: a chloro; a fluoro; a hydroxy; a cyano; a carboxy; a carbalkoxy; a nitro; an acylamino group (for example, an acetylamino group), carbamoyl, sulfonyl, sulfamoyl, sulfonamido, acyloxy (for example, an acetoxy group or a benzoyloxy group), or an oxycarbonyl group (for example, a methoxycarbonyl group, etc.), any of which may have 1 to 18 (or 1 to 10, 1 to 6, or 1 to 2) carbon atoms.
  • L may particularly have a total of 1 to 20 (or 1 to 10, or 1 to 4) atoms and be an alkylene group of which may have 1-5 (or 1, 2 or 3) intervening oxygen, sulfur or nitrogen atoms.
  • Substituents on L include, for example, a 1 to 10 (or 1 to 6, or 1 or 2) carbon alkoxy, a 1 to 10 (or 1 to 6, or 1 or 2) carbon atom alkyl sulfide, 0 to 10 (or 0 to 6, or 0 to 2) carbon amino, or with halogen.
  • L may particularly be an unsubstituted methine (that is, only one carbon atoms in length with no intervening heteroatoms) or a methine substituted with 1 to 12 (or 1, 2 or 3) carbon atom alkyl or alkoxy (either with or without 1 or 2 intervening oxygen atoms), or with a 0 to 6 (or 0, 1, 2, or 3) carbon atom amino, or a halogen (such as F or Cl).
  • R 5 , R 6 and R 7 are, independently: H; halogen; cyano; an alkyl group or alkoxy group; thioalkyl group; alkylamino or arylamino group; an aryl group or aryloxy group; or a heteroaryl group.
  • R 5 , R 6 and R 7 is an alkyl or alkoxy group it may, for example, have from 1 to 20 C atoms (or 1 to 10 or 1 to 6, such as methyl, ethyl, propyl, butyl or pentyl).
  • Suitable aryl groups, aryloxy groups or heteroaryl groups may be selected from such groups as described in connection with R 1 , R 2 and R 3 above.
  • Substituents on any of the foregoing groups for R 5 , R 6 and R 7 may be selected from among the substituents on corresponding groups for R 1 , R 2 and R 3 described above. Such substituents include alkoxy (particularly 1 to 6 carbon atoms), halogen (particularly Cl and F), and cyano. It is preferred that each of R 5 , R 6 and R 7 is selected from H or alkyl groups.
  • R 5 , R 6 and R 7 be different such that the carbon or silicon atom bearing those groups is asymmetric (a racemic carbon or silicon center).
  • the compound of formula (I) could have further racemic carbon centers.
  • R 1 , R 2 , R 3 or R 4 also contains an asymetric carbon (or any other substituent also contains an asymmetric carbon), such that there are two or more asymmetric carbons in the compound, diastereomers can then be formed. This means that the UV absorbing compound of formula (I) could then have more than one pair of enantiomers.
  • the compound should preferably have a 60/40 to 40/60 (preferably 50/50) ratio of at least two enantiomers (although it can have, for example a 60/40 to 40/60 ratio of enantiomers in each of two sets of enantiomers).
  • UV absorbing compounds are specifically contemplated which are of formula (I) (including formula (Ia), (Ib) and all the specific examples below) but in which the entire linkage of --N--X--(L) p --A* is on the 5- or 6- position of the benzene ring of the benzotriazole.
  • the 4'-position of the hydroxyphenyl ring could be substituted with any of those substituents described above for R 1 or R 2 .
  • compounds are specifically contemplated, they are not considered compounds of the present invention (which require the --N--X--(L) p --A* to be in the 4'-position as shown in formula (I).
  • UV absorbing compounds of formula (I) can be prepared from the chromophore of formula (III), below.
  • the compounds of formula (III) can be readily synthesized from inexpensively available starting materials such as o-nitroaniline, 4-chloro-2-nitroaniline and m-amino or m-aminoalkyl substituted phenols by procedures known in the art (See, for example, U.S. Pat. No. 3,813,255).
  • the 2-(2'-hydroxy-4'-aminophenyl)benzotriazole can be made by reacting 2-nitrobenzenediazonium chloride with 3-aminophenol followed by reductive ring closure of the azo dye to the desired benzotriazole.
  • the carbamate containing UV compounds of the present invention could alternatively be synthesized by condensing the amino-substituted benzotriazole compounds with the corresponding alcohol counterpart in presence of Di-2-pyridyl carbonate (“DPC") (structure (IV) shown below) as a condensing agent in the presence of an inert solvent such as ethyl acetate or tetrahydrofuran.
  • DPC Di-2-pyridyl carbonate
  • an inert solvent such as ethyl acetate or tetrahydrofuran.
  • Photographic elements according to the present invention will typically have at least one light sensitive silver halide emulsion layer and a non-light sensitive layer, with the ultraviolet absorbing compound of formula (I) being typically (but not necessarily) located in the non-light sensitive layer. More preferably, a photographic element of the present invention will have the non-light sensitive layer containing the ultraviolet absorbing compound located above all light sensitive layers. However, it is also contemplated that the ultraviolet absorbing compound can additionally be present in another layer, such as an interlayer (or even a light sensitive layer), particularly an interlayer located between red and green sensitive layers in an element having blue, green and red-sensitive layers coated in that order, on a support (particularly a paper support). Any layer of the photographic element in which the UV absorbing compounds of formula (I) are located will normally be a gel layer, and the UV absorbing compound may particularly be dispersed therein using a coupler solvent with or without additional ethyl acetate.
  • the UV absorbing compounds can be directly dispersed in the element or dispersed therein in droplets of a solvent dispersion.
  • the UV absorbing compounds of formula (I) can be loaded into a polymer latex by themselves or with other compounds such as high boiling point organic solvents or monomeric UV absorbing compounds.
  • "Loading" a polymer latex is generally described in U.S. Pat. No. 4,199,363 for example. Loading of a polymer latex is also described, for example, in U.S. Pat. Nos. 4,203,716, 4,214,047, 4,247,627, 4,497,929 and 4,608,424.
  • UV absorbing compounds of the present invention are preferably used by themselves in a photographic element. However, they may be used in conjunction with other UV absorbing compounds if desired, such as other benzotriazole based UV absorbers.
  • conventional UV absorbing agents which can be used include: 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di(1,1-dimethylbenzyl)-phenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert
  • UV absorbing agents such as p-hydroxybenzoates, phenylesters of benzoic acid, salicylanilides and oxanilides, diketones, benzylidene malonate, esters of ⁇ -cyano-cinnamic acid, and organic metal photostabilizers, and others, as described in J. F. Rabek, Photostabilization of Polymers, Principles and Applications, Elsevier Science Publishers LTD, England, page 202-278(1990).
  • the UV absorbing compound is incorporated into the photographic element (typically into a gelatin gel thereof) in an amount of between 0.2 g/m 2 to 10 g/m 2 , and more preferably between 0.5 g/m 2 to 5.0 g/m 2 .
  • the weight ratio of high boiling, water immiscible organic solvent to UV absorbing compound is preferably between 0.1 to 5.0 (that is, 0.1/1 to 5.0/1 of solvent/UV absorbing compound), and more preferably between 0.2 to 3.0 (that is, 0.2/1 to 3.0/1 of solvent/UV absorbing compound).
  • the UV absorbing compound of formula (I) is provided in any one or more of the layers (for example, a hydrophilic colloid layer such as a gelatin layer) of a photographic light-sensitive material (for example, a silver halide photographic light-sensitive material), such as a surface protective layer, an intermediate layer or a silver halide emulsion layer, and the like.
  • a photographic light-sensitive material for example, a silver halide photographic light-sensitive material
  • the UV absorbing compound of formula (I) with/without other UV absorbing compounds may be positioned above and/or below the red sensitive layer (typically adjacent to it), the red sensitive layer typically being the uppermost light sensitive layer in color paper, or even completely or partially within the red sensitive layer.
  • the UV absorbing compound is typically provided in a given layer of a photographic element by coating the hydrophilic colloid material (such as a gelatin emulsion) which contains the latex, onto a support or another previously coated layer forming part of the element.
  • the photographic elements made by the method of the present invention can be single color elements or multicolor elements.
  • Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum.
  • Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art.
  • the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
  • a typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
  • the element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like. All of these can be coated on a support which can be transparent or reflective (for example, a paper support).
  • Photographic elements of the present invention may also usefully include a magnetic recording material as described in Research Disclosure, Item 34390, November 1992, or a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support as in U.S. Pat. Nos. 4,279,945 and 4,302,523.
  • the element typically will have a total thickness (excluding the support) of from 5 to 30 microns. While the order of the color sensitive layers can be varied, they will normally be red-sensitive, green-sensitive and blue-sensitive, in that order on a transparent support, (that is, blue sensitive furthest from the support) and the reverse order on a reflective support being typical.
  • the present invention also contemplates the use of photographic elements of the present invention in what are often referred to as single use cameras (or "film with lens” units). These cameras are sold with film preloaded in them and the entire camera is returned to a processor with the exposed film remaining inside the camera. Such cameras may have glass or plastic lenses through which the photographic element is exposed.
  • the silver halide emulsions employed in the elements of this invention can be either negative-working, such as surface-sensitive emulsions or unfogged internal latent image forming emulsions, or direct positive emulsions of the unfogged, internal latent image forming type which are positive working when development is conducted with uniform light exposure or in the presence of a nucleating agent.
  • negative-working such as surface-sensitive emulsions or unfogged internal latent image forming emulsions
  • direct positive emulsions of the unfogged, internal latent image forming type which are positive working when development is conducted with uniform light exposure or in the presence of a nucleating agent.
  • Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through V.
  • Color materials and development modifiers are described in Sections V through XX.
  • Vehicles which can be used in the elements of the present invention are described in Section II, and various additives such as brighteners, antifoggants, stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections VI through X and XI through XIV. Manufacturing methods are described in all of the sections, other layers and supports in Sections XI and XIV, processing methods and agents in Sections XIX and XX, and exposure alternatives in Section XVI.
  • a negative image can be formed.
  • a positive (or reversal) image can be formed although a negative image is typically first formed.
  • the photographic elements of the present invention may also use colored couplers (for example to adjust levels of interlayer correction) and masking couplers such as those described in EP 213 490; Japanese Published Application 58-172,647; U.S. Pat. No. 2,983,608; German Application DE 2,706,117C; U.K. Patent 1,530,272; Japanese Application A-113935; U.S. Pat. No. 4,070,191 and German Application DE 2,643,965.
  • the masking couplers may be shifted or blocked.
  • the photographic elements may also contain materials that accelerate or otherwise modify the processing steps of bleaching or fixing to improve the quality of the image.
  • Bleach accelerators described in EP 193 389; EP 301 477; U.S. Pat. Nos. 4,163,669; 4,865,956; and 4,923,784 are particularly useful.
  • nucleating agents, development accelerators or their precursors UK Patent 2,097,140; U.K. Patent 2,131,188; electron transfer agents (U.S. Pat. Nos.
  • antifogging and anti color-mixing agents such as derivatives of hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming couplers.
  • the elements may also contain filter dye layers comprising colloidal silver sol or yellow and/or magenta filter dyes and/or antihalation dyes (particularly in an undercoat beneath all light sensitive layers or in the side of the support opposite that on which all light sensitive layers are located) either as oil-in-water dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with "smearing" couplers (for example as described in U.S. Pat. No. 4,366,237; EP 096 570; U.S. Pat. Nos. 4,420,556; and 4,543,323.) Also, the couplers may be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. Pat. No. 5,019,492.
  • the photographic elements may further contain other image-modifying compounds such as "Developer Inhibitor-Releasing” compounds (DIR's).
  • DIR's Developer Inhibitor-Releasing compounds
  • DIR compounds are also disclosed in "Developer-Inhibitor-Releasing (DIR) Couplers for Color Photography," C. R. Barr, J. R. Thirtle and P. W. Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969), incorporated herein by reference.
  • the emulsions and materials to form elements of the present invention may be coated on pH adjusted support as described in U.S. Pat. No. 4,917,994; with epoxy solvents (EP 0 164 961); with additional stabilizers (as described, for example, in U.S. Pat. Nos. 4,346,165; 4,540,653 and 4,906,559); with ballasted chelating agents such as those in U.S. Pat. No. 4,994,359 to reduce sensitivity to polyvalent cations such as calcium; and with stain reducing compounds such as described in U.S. Pat. Nos. 5,068,171 and 5,096,805.
  • the silver halide used in the photographic elements may be silver iodobromide, silver bromide, silver chloride, silver chlorobromide, silver chloroiodobromide, and the like.
  • the silver halide used in the photographic elements of the present invention may contain at least 90% silver chloride or more (for example, at least 95%, 98%, 99% or 100% silver chloride).
  • some silver bromide may be present but typically substantially no silver iodide.
  • Substantially no silver iodide means the iodide concentration would be no more than 1%, and preferably less than 0.5 or 0.1%.
  • the silver chloride could be treated with a bromide source to increase its sensitivity, although the bulk concentration of bromide in the resulting emulsion will typically be no more than about 2 to 2.5% and preferably between about 0.6 to 1.2% (the remainder being silver chloride).
  • the foregoing % figures are mole %.
  • the type of silver halide grains preferably include polymorphic, cubic, and octahedral.
  • the grain size of the silver halide may have any distribution known to be useful in photographic compositions, and may be ether polydipersed or monodispersed.
  • Tabular grain silver halide emulsions may also be used.
  • Tabular grains are those with two parallel major faces each clearly larger than any remaining grain face and tabular grain emulsions are those in which the tabular grains account for at least 30 percent, more typically at least 50 percent, preferably >70 percent and optimally >90 percent of total grain projected area.
  • the tabular grains can account for substantially all (>97 percent) of total grain projected area.
  • the emulsions typically exhibit high tabularity (T), where T (that is, ECD/t 2 ) >25 and ECD and t are both measured in micrometers ( ⁇ m).
  • the tabular grains can be of any thickness compatible with achieving an aim average aspect ratio and/or average tabularity of the tabular grain emulsion.
  • the tabular grains satisfying projected area requirements are those having thicknesses of ⁇ 0.3 ⁇ m, thin ( ⁇ 0.2 ⁇ m) tabular grains being specifically preferred and ultrathin ( ⁇ 0.07 ⁇ m) tabular grains being contemplated for maximum tabular grain performance enhancements.
  • thin tabular grains typically up to 0.5 ⁇ m in thickness, are contemplated.
  • High iodide tabular grain emulsions are illustrated by House U.S. Pat. No. 4,490,458, Maskasky U.S. Pat. No. 4,459,353 and Yagi et al EPO 0 410 410.
  • Tabular grains formed of silver halide(s) that form a face centered cubic (rock salt type) crystal lattice structure can have either ⁇ 100 ⁇ or ⁇ 111 ⁇ major faces.
  • Emulsions containing ⁇ 111 ⁇ major face tabular grains, including those with controlled grain dispersities, halide distributions, twin plane spacing, edge structures and grain dislocations as well as adsorbed ⁇ 111 ⁇ grain face stabilizers, are illustrated in those references cited in Research Disclosure I, Section I.B.(3) (page 503).
  • the silver halide grains to be used in the invention may be prepared according to methods known in the art, such as those described in Research Disclosure I and James, The Theory of the Photographic Process. These include methods such as ammoniacal emulsion making, neutral or acidic emulsion making, and others known in the art. These methods generally involve mixing a water soluble silver salt with a water soluble halide salt in the presence of a protective colloid, and controlling the temperature, pAg, pH values, etc, at suitable values during formation of the silver halide by precipitation.
  • the silver halide to be used in the invention may be advantageously subjected to chemical sensitization with noble metal (for example, gold) sensitizers, middle chalcogen (for example, sulfur) sensitizers, reduction sensitizers and others known in the art.
  • noble metal for example, gold
  • middle chalcogen for example, sulfur
  • reduction sensitizers and others known in the art.
  • Compounds and techniques useful for chemical sensitization of silver halide are known in the art and described in Research Disclosure I and the references cited therein.
  • Photographic emulsions generally include a vehicle for coating the emulsion as a layer of a photographic element.
  • Useful vehicles include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives (for example, cellulose esters), gelatin (for example, alkali-treated gelatin such as cattle bone or hide gelatin, or acid treated gelatin such as pigskin gelatin), gelatin derivatives (for example, acetylated gelatin, phthalated gelatin, and the like), and others as described in Research Disclosure I.
  • Also useful as vehicles or vehicle extenders are hydrophilic water-permeable colloids.
  • the vehicle can be present in the emulsion in any amount useful in photographic emulsions.
  • the emulsion can also include any of the addenda known to be useful in photographic emulsions.
  • Chemical sensitizers such as active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, rhodium, ruthenium, phosphorous, or combinations thereof. Chemical sensitization is generally carried out at pAg levels of from 5 to 10, pH levels of from 5 to 8, and temperatures of from 30° to 80° C., as illustrated in Research Disclosure, June 1975, item 13452 and U.S. Pat. No. 3,772,031.
  • the silver halide may be sensitized by sensitizing dyes by any method known in the art, such as described in Research Disclosure I.
  • the dye may be added to an emulsion of the silver halide grains and a hydrophilic colloid at any time prior to (for example, during or after chemical sensitization) or simultaneous with the coating of the emulsion on a photographic element.
  • the dye/silver halide emulsion may be mixed with a dispersion of color image-forming coupler immediately before coating or in advance of coating (for example, 2 hours).
  • Photographic elements of the present invention are preferably imagewise exposed using any of the known techniques, including those described in Research Disclosure I, section XVI. This typically involves exposure to light in the visible region of the spectrum, and typically such exposure is of a live image through a lens, although exposure can also be exposure to a stored image (such as a computer stored image) by means of light emitting devices (such as light emitting diodes, CRT and the like).
  • a stored image such as a computer stored image
  • Photographic elements comprising the composition of the invention can be processed in any of a number of well-known photographic processes utilizing any of a number of well-known processing compositions, described, for example, in Research Disclosure I, or in T. H. James, editor, The Theory of the Photographic Process, 4th Edition, Macmillan, New York, 1977.
  • the element is first treated with a black and white developer followed by treatment with a color developer to produce a positive dye image.
  • the first developer is a color developer so as to produce a negative dye image.
  • Preferred color developing agents are p-phenylenediamines. Especially preferred are:
  • the UV-VIS data of (VI) indicates a hypsochromic shift in its ⁇ max as well as lower molar extinction coefficient. This may be corrected by introducing a Cl-- or a F-- substituent at 5-position in the benzo ring and substituting the ethyl group of R 4 with electron-withdrawing groups such as trifluormethyl or any perfluoroalkyl group.
  • This comparative compound is lacking a racemic carbon center, otherwise it is an exact match with the inventive compound (V) having the same total number of atoms the same in both.
  • This compound was made as a comparative example with a branched chain but lacking a racemic carbon center. As shown in Table 1, branching of the chain only does not provide a compound with the same performance as an inventive compound having a racemic center in the 4'-Carbamato, such as compound (V).
  • ⁇ max is the wavelength of maximum absorption (measured in MeOH as indicated in the Table)
  • ⁇ max is the extinction coefficient
  • the half bandwidth is the width of the absorption peak centered about ⁇ max as measured at one-half the maximum absorption ⁇ max . All of the foregoing were measured in methanol.
  • Table 1 illustrates the higher melting character of the comparative examples related to prior arts. As a result, they are prone to crystallize out in the dispersion and/or coating even if they have racemic chains particularly in primary carboxamido substituted compounds.
  • the dispersion is inspected microscopically for general particle size and crystallinity, and coated @ 1.16 ⁇ 10 -4 moles/ft 2 on an acetate base in a two layer SOC-type format, allowed to dry and the coating is also inspected microscopically for crystallinity (See Table 2).
  • Fresh coated spectral absorption data are recorded using a Perkin-Elmer Lambda 4C High Performance UV-VIS Spectrophotometer, and coated samples are HID (50 Klux Daylight; 315-700 nm) and HIS (50 Klux Sunshine; 280-700 nm) tested and compared to fresh data in order to obtain UV absorber intrinsic light stability information.
  • HID 50 Klux Daylight
  • HIS 50 Klux Sunshine
  • FIGS. 1& 2 Absorption spectra for various of the compounds were obtained in solution and in coating as described below and are shown in FIGS. 1& 2.
  • FIG. 1 shows the normalized absorption spectra in methanolic solution for a mixture of comparative control compounds II-A and II-B (solid line), as well as for the inventive compound V (dotted line).
  • FIG. 2 shows the absorption spectra in coating for inventive compound and the control compounds in total transmission mode of the spectrophotometer. Note from FIG. 1 that the inventive UV absorbing compound has about the same absorbance as a commonly used mixture of control UV absorbing compounds II-A/II-B in the important region of about 330-370 nm.
  • inventive compound has steeper slope at its longer wavelengths of absorption (that is, near 380 nm) and particularly drop to a lower absorption at their longest wavelength of the absorption, than does the mixture of II-A/II-B.
  • inventive UV absorbing compound exhibits, in addition to a steeper slope, a far higher extinction coefficient than comparative control compounds II-A/II-B as measured from fresh coating of their respective dispersions.
  • Microscopic observations for crystallinity in experimental UV absorber dispersions and coatings of these materials and their absorption spectra were performed as described here.
  • Microscopy is undertaken in the preparation of dispersions of experimental materials in order to provide an initial indication of physical properties such as general particle size and stability (that is, is the particular material susceptible to crystallize).
  • the microscopic particle size characterizations are performed using oil immersion optics ⁇ 1000 ⁇ microscopy, and ⁇ 200 ⁇ cross-polarized microscopy is used for crystal characterization.
  • Microscopic evaluation of the coatings is also undertaken because an acceptable non-crystalline dispersion may recrystallize in the coated format.
  • Table 2 illustrates how UV absorbing compound V of the present invention did not form any detectable crystals either in dispersion or in coating.
  • the compound VII being an exact match in terms of number of atoms and position of carbamato group attachment in the hydroxyphenyl ring, but lacking a racemic carbon center did not even dissolve in the dispersion.
  • the presence of a racemic carbon center in comparative compound X did influence it to go in the dispersion. However, this compound crystallized out in the coating.
  • Intrinsic light stability data for inventive UV absorber compound V are summarized in Table 3.
  • a combination of the compounds II-A & II-B has been used as a Control in each coating set.
  • the optical density loss, relative to the control coatings, was measured at 350 nm from coating spectral data.
  • carboxamido substituted benzotriazole examples (Compound Numbers XI through XV) regardless of the characteristics of the attached carbon chains had somewhat deeper hue, lower extinction coefficient and crystallized out in dispersion or in coating.
  • This observation further illustrates that the benzotriazole compounds, which could be used in a conventional dispersion format satisfying the criteria for color photographic paper, exhibit superior performance when they fall under the formula (I) of the present invention (that is, they contain a racemic carbamato substitutent at 4'-position in the hydroxyphenyl ring).
  • the present invention also specifically contemplates multilayer photographic elements as described in Research Disclosure, February 1995, Item 37038 (pages 79-115). Particularly contemplated is the use of any of the enantiomeric mixtures of formula (I) (particularly a 50/50 mixture of the two enantiomers) in such elements. Particularly, a 50/50 enantiomeric mixture of any one of the compounds in Tables A and B or Compounds V and VI, may be used as the UV absorbing compound in an overcoat of each of the photographic elements described in detail in Sections XVII through XXII of that Research Disclosure.

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DE69601384T DE69601384T2 (de) 1995-04-26 1996-04-15 Auf Benzotriazol basierende UV-Absorber und photographische Elemente, welche diese enthalten
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US5739348A (en) * 1996-10-23 1998-04-14 Eastman Kodak Company Method of synthesizing tert-amido-substituted 2-(2'-hydroxyphenyl) benzotriazole compounds in a one-step process
WO1998023252A1 (en) * 1996-11-22 1998-06-04 Ciba Specialty Chemicals Holding Inc. Use of selected benzotriazole derivatives for protecting human and animal skin and hair from the harmful effects of uv radiation
US5766834A (en) * 1996-05-17 1998-06-16 Eastman Kodak Company Photographic element containing ultraviolet absorbing polymer
US5914223A (en) * 1997-03-12 1999-06-22 Eastman Kodak Company Photographic element with outer layer having improved physical performance
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US6586057B1 (en) * 1999-09-29 2003-07-01 Fuji Photo Film Co., Ltd. Optical filter comprising transparent support and filter layer containing dye and binder polymer
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US20060014809A1 (en) * 2004-05-25 2006-01-19 Metabolex, Inc. Substituted triazoles as modulators of PPAR and methods of their preparation
US20060014785A1 (en) * 2004-05-25 2006-01-19 Metabolex, Inc. Bicyclic, substituted triazoles as modulators of ppar and methods of their preparation
US7078421B2 (en) 2002-03-20 2006-07-18 Metabolex, Inc. Substituted phenylacetic acids
US20070072858A1 (en) * 2005-09-23 2007-03-29 Metabolex, Inc. Process for the stereoselective preparation of (-)-halofenate and derivatives thereof
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US6653484B2 (en) 1996-07-18 2003-11-25 Ciba Specialty Chemicals Corporation Polyoxyalkylene substituted and bridged benzotriazole derivatives
US5739348A (en) * 1996-10-23 1998-04-14 Eastman Kodak Company Method of synthesizing tert-amido-substituted 2-(2'-hydroxyphenyl) benzotriazole compounds in a one-step process
US5683861A (en) * 1996-10-23 1997-11-04 Eastman Kodak Company Benzotriazole-based UV absorbers and photographic elements containing them
EP0838724A3 (en) * 1996-10-23 1999-02-03 Eastman Kodak Company Benzotriazole-based UV absorbers and photographic elements containing them
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EP0740198B1 (en) 1999-01-20
DE69601384T2 (de) 1999-07-15
EP0740198A3 (en) 1997-04-02
DE69601384D1 (de) 1999-03-04
EP0740198A2 (en) 1996-10-30
JPH08304957A (ja) 1996-11-22

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